Synthesis and structural characterisation of ruthenium and osmium carbonyl clusters containing organomercurials

Abstract

Reaction of the activated cluster [Os₃(CO)₁₀(NCMe)₂] with [PhHgS(C₅H₄N)] afforded two new Os–Hg clusters cis-[Os(CO)₄{Os₃(CO)₁₀(µ-η²-SC₅H₄N)(µ-Hg)}₂] 1 and [{Os₃(CO)₁₀(µ-η²-SC₅H₄N)}₂(µ₄-Hg)] 2 in 25 and 30% yields, respectively. Cluster 1 consists of two {Os₃(CO)₁₀(µ-η²-SC₅H₄N)(µ-Hg)} subunits bonded to a central Os(CO)₄ moiety in a cis configuration. Cluster 2 comprises two skewed Os–Hg metal butterflies sharing a common wingtip Hg atom. Treatment of the same organomercurial with [Ru₃(CO)₁₀(NCMe)₂] produced the cluster compound cis-[Ru(CO)₄{Ru₃(CO)₉(µ-η³-SC₅H₄N)(µ-Hg)}₂] 3 (48%). This has a metal skeleton similar to that of 2 with the {S(C₅H₄N)} ligand moiety bonding to the ruthenium atoms in a µ-η³ fashion. Treatment of [Os₃(CO)₁₀(NCMe)₂] with [PhHg(mbt)] (Hmbt = 2-mercaptobenzothiazole) afforded [{Os₃(CO)₁₀(µ-η²-mbt)}₂(µ₄-Hg)] 4 (35%) and [Os₃(CO)₁₀(µ-η²-mbt)(µ-η²-Hg(mbt)] 5 (20%). Cluster 4 is very similar to 2, but the S(C₅H₄N) ligand is replaced by the mbt ligand, while 5 consists of an Os₃ triangle having one edge spanned by both [µ-η²-mbt] and [µ-η²-Hg(mbt)] moieties. The reaction of [Os₅C(CO)₁₅] and [Ru₃(CO)₁₂] with another class of organomercurial (diphenylthiocarbazono)phenylmercury reagent [PhHgL′] [L′ = SC(N[double bond, length half m-dash]NPh)([double bond, length half m-dash]NNHPh)] containing a N[double bond, length half m-dash]N functionality under thermal conditions produced [{Os₅C(CO)₁₄(µ-η²-SPh)}₂(µ₄-Hg)] 6 (26%) and [{Os₅C(CO)₁₄(µ-η²-L′)}₂(µ₄-Hg)] 7 (34%) and [Ru₂(CO)₄Ph{µ-η²-C(O)Ph}(µ₂-S)(µ-η²-L′)] 8 (15%), [Ru₂(CO)₄{C(O)Ph}{µ-η²-C(O)Ph}(µ₂-S)(µ-η²-L′)] 9 (15%) and [{Ru(CO)₂Ph}₂(µ-η²-L′)] 10 (45%), respectively. In clusters 6 and 7, two {Os₅C(CO)₁₄} subunits linked by a common wingtip mercury atom, are bonded with both µ-η²-SPh in 6 and µ-η²-L′ in 7. However, in the case of complexes 8, 9 and 10, only binuclear ruthenium carbonyl complexes formed instead of the expected formation of mixed-metal clusters. Complexes 1–10 result from the cleavage of both Hg–C and Hg–S bonds in the parent organomercury species. All these complexes have been fully characterized by both spectroscopic and crystallographic techniques.

References

1. M. Ferrer, A. Perales, O. Rossel and M. Seco, J. Chem. Soc., Chem. Commun., 1990, 1447.
2. L. N. Zakharov, Y. T. Struchkov, S. N. Titova, V. T. Bychkov, G. A. Domrachev and G. A. Razumaez, Cryst. Struct. Commun., 1980, 9, 549.
3. A. Bianchini and L. J. Farrugia, Organometallics, 1992, 11, 540.
4. E. Rosenberg, D. Ryckman, I. N. Hsu and R. W. Gellert, Inorg. Chem., 1986, 25, 194.
5. L. H. Gade, Angew. Chem., Int. Ed. Engl., 1993, 32, 24.
6. (a) Y. K. Au and W. T. Wong, J. Chem. Soc., Dalton Trans., 1995, 1389; (b) Y. K. Au and W. T. Wong, J. Chem. Soc., Dalton Trans., 1996, 899; (c) Y. K. Au and W. T. Wong, Inorg. Chem., 1997, 36, 2092.
7. J. W. S. Hui and W. T. Wong, J. Chem. Soc., Dalton Trans., 1997, 2445; J. W. S. Hui and W. T. Wong, J. Chem. Soc., Dalton Trans., 1998, 2065.
8. C. Cathey, J. Lewis, P. R. Raithby and M. C. Ramirez de Arellano, J. Chem. Soc., Dalton Trans., 1994, 3331.
9. A. Bianchini and L. J. Farrugia, Organometallics, 1992, 11, 540.
10. S. Hajela, B. M. Novak and E. Rosenberg, Organometallics, 1989, 8, 468.
11. M. R. Churchill and B. G. Deboer, Inorg. Chem., 1977, 16, 878.
12. A. J. Deeming, K. I. Hardcastle and M. Karim, Inorg. Chem., 1992, 31, 4792.
13. M. R. Churchill and R. A. Lachewycz, Inorg. Chem., 1979, 18, 3261.
14. P. L. Andreu, J. A. Cabeza, A. Llamazares and V. Riera, J. Organomet. Chem., 1991, 420, 431.
15. B. F. G. Johnson, W. L. Kwik, J. Lewis, P. R. Raithby and V. P. Saharan, J. Chem. Soc., Dalton Trans., 1991, 1037.
16. B. F. G. Johnson, J. Lewis, S. W. Sankey, K. Wong, M. McPartlin and W. J. H. Nelson, J. Organomet. Chem., 1980, 191, C3.
17. P. F. Jackson, B. F. G. Johnson, J. Lewis and J. N. Nicholls, J. Chem. Soc., Chem. Commun., 1980, 564.
18. J. S. Bradley, R. L. Pruett, E. Hill, G. B. Ansell, M. E. Leonowicz and M. A. Modrick, Organometallics, 1982, 1, 748.
19. S. M. Lee and W. T. Wong, J. Cluster Sci., 1996, 7, 37.
20. R. O. Gould, T. A. Stephenson and D. A. Tocher, J. Organomet. Chem., 1984, 263, 375.
21. A. J. Arce, P. Arrojo, A. J. Deeming and Y. de Sanctis, J. Chem. Soc., Chem. Commun., 1991, 1491.
22. N. Lugan, G. Lavigne and J. J. Bonnet, Inorg. Chem., 1986, 25, 9.
23. D. M. P. Mingos, J. Chem. Soc., Chem. Commun., 1982, 706.
24. M. R. Churchill, F. J. Hollander and J. P. Hutchison, Inorg. Chem., 1977, 16, 2655.
25. M. R. Burns and J. L. Hubbard, J. Am. Chem. Soc., 1994, 116, 9514.
26. F. S. Kong and W. T. Wong, unpublished results.
27. A. Castineiras, W. Hiller, J. Strahle, J. Bravo, J. S. Casas, M. Gayoso and J. Sordo, J. Chem. Soc., Dalton Trans., 1986, 1945.
28. J. Bravo, J. S. Casas, M. Castano, M. Gayoso, Y. P. Mascarenhas, A. Sanchez, C. de. O. P. Santos and J. Sordo, Inorg. Chem., 1985, 24, 3435.
29. D. T. Cromer and J. T. Waber, International Tables for X-Ray Crystallography, Kynoch Press, Birmingham, 1974, vol. 4, (a) Table 22B; (b) Table 2.3.1.
30. M. C. Burla, M. Camalli, G. Cascarano, C. Giacovazzo, G. Polidori, R. Spagna and D. Viterbo, J. Appl. Crystallogr., 1989, 22, 389.
31. A. Altomare, M. C. Burla, M. Camalli, M. Cascarano, G. Giacovazzo, A. Guagliardi and G. Polidori, SIR 92, J. Appl. Crystallogr., 1994, 27, 435.
32. G. M. Sheldrick, SHELXS 86, Program for Crystal Structure Solution, Acta Crystallogr., Sect. A, 1990, 46, 467.
33. DIRDIF94: B. T. Beurskens, G. Admiroal, G. Beurskens, W. P. Bosman, R. de Gelder, R. Iserel and J. M. M. Smits, Technical Report of the Crystallography Laboratory, University of Nijmegen, 1994.
34. TEXSAN, Crystal Structure Analysis Package, Molecular Structure Corporation, 1985 and 1992.